Grease composition

ABSTRACT

The invention is an improved grease composition comprising a major proportion of a grease, a hydroxy-containing soap thickener and a minor amount of a compound prepared by reacting a boron compound with an organic compound containing oxygen, sulfur and/or nitrogen or mixtures thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of each of the following copending applications, each of which, as well as the application parent thereto, is incorporated herein by reference:

Application Ser. No. 774,873, filed Sep. 12, 1985, now abandoned, which is a continuation of application Ser. No. 641,077, filed Aug. 15, 1984, now abandoned, which is a continuation-in-part of U.S. application Ser. No. 587,328, filed Mar. 7, 1984, now abandoned.

U.S. application Ser. No. 641,078, filed Aug. 15, 1984, now abandoned, which is a continuation-in-part of application Ser. No. 577,454, filed Feb. 6, 1984, now abandoned.

U.S. application Ser. No. 831,073, filed Feb. 18, 1986, now abandoned, which is a continuation of Ser. No. 643,344, filed Aug. 22, 1984, now abandoned.

U.S. application Ser. No. 643,346, filed Aug. 22, 1984, now U.S. Pat. No. 4,600,517.

U.S. application Ser. No. 792,168, filed Oct. 25, 1985, now abandoned, which is a continuation of application Ser. No. 643,347 filed Aug. 22, 1984, now abandoned.

U.S. application Ser. No. 769,827, filed Aug. 27, 1985, now abandoned.

U.S. application Ser. No. 769,826, filed Aug. 27, 1985, now U.S. Pat. No. 4,743,386; which is a continuation-in-part of application Ser. No. 682,579, filed Dec. 17, 1984, now abandoned, which is a continuation of application Ser. No. 445,883, filed Dec. 1, 1982, now abandoned, which is a continuation-in-part of application Ser. No. 638,609, now U.S. Pat. No. 4,571,248, filed Aug. 7, 1984, which is a division of application Ser. No. 456,880, filed Jan. 10, 1983, now U.S. Pat. No. 4,486,321.

U.S. application Ser. No. 769,912, filed Aug. 27, 1985, now abandoned.

U.S. application Ser. No. 769,837, filed Aug. 27, 1985 now U.S. Pat. No. 4,655,948.

U.S. application Ser. No. 641,079, filed Aug. 15, 1984, now U.S. Pat. No. 4,582,617, which is a continuation-in-part of U.S. application Ser. No. 519,878, filed Aug. 3, 1983, now abandoned.

U.S. application Ser. No. 319,841, filed Mar. 7, 1989, now U.S. Pat. No. 4,961,868.

FIELD OF THE INVENTION

The invention is concerned with novel grease compositions. It more particularly relates to an improved grease composition comprising an oil of lubricating viscosity, a thickener of which at least about 15% thereof is a hydroxy-containing soap thickener, a borated derivative of an organic compound containing optionally and preferably an oxygen, sulfur or nitrogen moiety or mixtures thereof which is reactive with a borating agent, and said borated derivative can optionally contain any other element of the Periodic Chart, excluding zinc.

DISCUSSION OF THE PRIOR ART

Borated alkoxylated alcohols have been used in commercial lubricant formulations to provide improvement in lubricity properties. This is known from U.S. Pat. No. 3,711,411, which discloses hydraulic fluids containing such products.

It is known further that borated esters and related borates can be used in other areas. For example, U.S. Pat. No. 3,740,358 teaches a phenol-aldehyde foamable composition containing a boron compound, e.g. a material formed by reacting boric acid or boric oxide with an aliphatic hydroxyl-containing compound.

U.S. Pat. No. 2,160,917 discloses lubricants containing low molecular weight borate esters, e.g., borate esters containing from 4 to 12 carbon atoms. The disclosed borates include the tributyl and trilauryl borates. Other patents include U.S. Pat. No. 3,014,870 (to mixtures of amine and certain boronic mono-or diesters); U.S. Pat. No. 3,108,966 (aryl boronic esters and thio acid ester lubricants); U.S. Pat. No. 3,133,951 (fuels containing dialkyl boron esters); U.S. Pat. No. 3,347,793 (tertiaryalkyl boron esters) and U.S. Pat. No. 3,509,054 (esters or boron acids with 2,6-dialkyl-phenols).

From U.S. Pat No. 4,328,113 it is also known that borated amines, such as borated hydrocarbyl mon-and diamines, are useful as friction reducers in lubricants, especially in lubricating oils.

Vicinal hydroxyl-containing alkyl carboxylates such as glycerol monoolerate have found use as lubricity additives. U.S. Pat. No. 2,788,326 discloses some of the esters suitable for the present invention, e.g., glycerol monooleate, as minor components of lubricating oil compositions. U.S. Pat. No. 3,235,498 discloses, among others, the same ester as just mentioned, as an additive to other oils. U.S. Pat. No. 2,443,578 teaches esters wherein the free hydroxyl is found in the acid portion, as for example, in tartaric acid.

The above patents, as are numerous others, are directed to the use of such esters as additives. Other patents, such as U.S. Pat. Nos. 2,798,083; 2,820,014; 3,115,519; 3,282,917 and 3,309,318 as well as an article by R. R. Barnes et al. entitled "Synthetic Ester Lubricants" in Lubrication Engineering, August, 1975, pp. 454-457, teach lubricants prepared by polyhydric alcohols and acid containing no hydroxyl other than those associated with the acid function.

U.S. Pat. No. 4,374,032 corresponding to application Ser. No. 134,849, filed Mar. 28, 1980, discloses the use of borated adducts of oxazolines as a component of lubricating oils. U.S. Pat. No. 4,374,032 is incorporated herein by reference.

U.S. Pat. No. 4,389,322 discloses the use of borated adducts of ethoxylated amides as a component of lubricating oils or greases. U.S. Pat. No. 4,389,322 is incorporated herein by reference.

The borated adducts of ethoxylated amides are prepared from ethoxylated compounds having the following generalized structure: ##STR1## R is hydrocarbyl group having from about 1 to about 60 (preferably 8 to 30) carbon atoms; R may be alkyl, alkenyl, aralkyl, alkylaryl, etc; x and y may be the same or different and are each a whole number from 0 to about 15, preferably 1 to 5, but the sum of x and y must equal 1 or more, or more preferably, 2 or more. R⁴ is hydrogen or an alkyl or alkenyl radical of one to six carbon atoms and preferably is hydrogen or a methyl radical.

The borated derivatives can be prepared according to the disclosure in U.S. Pat. No. 4,490,256 which is incorporated herein by reference or by treating the described amides with boric acid optionally in alcoholic solvents such as butanol or pentanol, or optionally hydrocarbon solvents such as benzene, toluene, xylene or mixtures thereof. Reaction temperatures of 70° to 260° C. can be used but 110° C. to 170° is preferred. Reaction times can be 1 to 10 hours or more. Up to a stoichiometric amount or an excess of boric acid can be used to produce a derivative containing 0.05% to 8% or more by weight of boron. Other methods are also available to make similar borated derivatives. For example, the ethoxylated amides may also be borated through transesterification with a trialkyl borate such as tributyl borate (often in the presence of boric acid).

The publication "Manufacture and Application of Lubricating Grease by C. J. Boner (Reinhold Publishing Company) 1954, pp. 155 and 436, 437 disclose the use of lithium soaps in grease making. The publication "Lubricant Additive" by C. V. Smalheer et al (Leyuis-Hiles Co.) 1967, pp. 1-11, discloses the use of phosphonates and thiophosphonates as additives in lubricants. "Condensed Chemical Dictionary" 9th Edition, (Van Nostrand Reinhold Company) at pages 520 and 938 discloses the use of lithium hydroxystearate in grease making and zinc dialkyldithiophosphate as a lube oil additive.

These references, the publications by Boner and by Smalheer et al, and the "Condensed Chemical Dictionary" reference are incorporated herein by reference.

SUMMARY OF THE INVENTION

In accordance with the invention, there is provided an improved grease composition containing a major amount of a grease and a minor amount of the borated derivatives of an organic compound containing optionally and preferably an oxygen, sulfur, or nitrogen moiety or mixtures thereof which is reactive with a borating agent which may be boric acid, boric oxide, metaborate or an alkyl borate of the formula

    (R.sup.1 O).sub.x B(OH).sub.y

wherein x is 1 to 3, y is 0 to 2, their sum being 3, and R¹ is an alkyl group containing from 1 to 6 carbon atoms or any other suitable boronating compound containing boron and a thickener containing at least about 10-15% by weight of a hydroxy-containing soap thickener. The above boron-containing organic compound can contain additionally any of the other elements of the Periodic Table excluding zinc. We believe, however, that the major benefits arise from the organic boron moieties such as those organic borates containing at least (a) carbon, hydrogen, oxygen, boron and other optional elements, (b) carbon, hydrogen, nitrogen, boron and other optional elements and combinations of (a) and (b) above.

Preferably the organic compound is overborated. By "overborated" is meant the presence in the borated product of more than a stoichiometric amount of boron.

DESCRIPTION OF SPECIFIC EMBODIMENTS

Examples of the types of sulfur, oxygen, and/or nitrogen containing borated organic compounds are:

alkoxylated alcohols

long-chain and short-chain alcohols

diols, preferably vicinal diols

mono- or polyamines

hydrocarbyl esters

oxazoline compounds

phenolic- and/or thio-amine Mannich bases

catechol, catechol-alcohol borates compounds, and catechol-amine borate compounds.

Each of the specific embodiments can additionally contain carboxylic acid or ester groups, amide groups, metallic salts groups and other groups without significantly detracting from the above disclosed invention.

Preparation of most of these borated compounds is disclosed in the copending applications parent to this application, those applications having been incorporated herein by reference.

The Alkoxylated Alcohols

The borated alkoxylated alcohols are prepared by reacting an alkoxylated alcohol or mixtures of such alcohols having the formula

    RO(R.sup.1 O).sub.x H

wherein R is a hydrocarbyl group containing from 7 to 30 carbon atoms, preferably 9 to 18 carbon atoms, R¹ is a hydrocarbylene group containing from 2 to 4 carbon atoms and x is from 1 to 10, with a borating agent.

Long-Chain and Short-Chain Alcohols

In accordance with the invention, the long-chain and the borated short-chain alcohols are prepared by reacting an alcohol of the formula

    R.sup.2 OH

wherein R² is a C₁ to C₃₀ hydrocarbon group, or mixtures thereof, with the borating compound described below.

Preferably the alcohol is overborated. By "overboarated" is meant the presence in the borated product of more than a stoichiometric amount of boron. Up to 100% to 1000% or more excess boron can be used.

The hydrocarbyl group includes straight and branched chain aliphatic groups, cycloaliphatic groups, aralkyl groups and alkaryl groups.

R may be a linear or branched alkyl group or mixtures thereof. It may also be cycloaliphatic group, an alkaryl group, an aryl alkyl group or a linear or branched group having at least one unsaturated bond, i.e., an alkenyl group, or mixtures thereof. Among the short-chain alcohols, the mixed C₁ to C₁₁ groups are preferred, with the more preferred being mixed C₅ to C₁₁ groups.

Short-chain alcohols that can be used for boration include:

    ______________________________________                                         Chemical                                                                       Name      Common Name   Formula                                                ______________________________________                                         Methanol  Methyl alcohol                                                                               CH.sub.3 OH                                            Ethanol   Ethyl alcohol CH.sub.3 CH.sub.2 OH                                   1-Propanol                                                                               n-Propyl alcohol                                                                             CH.sub.3 CH.sub.2 CH.sub.2 OH                          2-Propanol                                                                               Isopropyl alcohol                                                                            (CH.sub.3).sub.2 CHOH                                  1-Butanol n-Butyl alcohol                                                                              CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 OH                 2-Methyl- Isobutyl alcohol                                                                             (CH.sub.3).sub.2 CHCH.sub.2 OH                         1-propanol                                                                     2-Butanol sec-Butyl alcohol                                                                            CH.sub.3 CH.sub.2 CHOHCH.sub.3                         2-Methyl- tert-Butyl alcohol                                                                           (CH.sub.3).sub.3 COH                                   2-propanol                                                                     1-Pentanol                                                                               n-Amyl alcohol                                                                               CH.sub.3 (CH.sub.2).sub.3 CH.sub.2 OH                  2-Pentanol                                                                               sec-Amyl alcohol                                                                             CH.sub.3 (CH.sub.2).sub.2 CHOHCH.sub.3                 3-Pentanol                                                                               Diethylmethanol                                                                              (CH.sub.3 CH.sub.2).sub.2 CHOH                         2-Methyl- Active amyl   CH.sub.3 CH.sub.2 CH(CH.sub.3)CH.sub.2 OH              1-butanol alcohol                                                              3-Methyl- Isoamyl alcohol                                                                              (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2 OH                1-butanol                                                                      2-Methyl- tert-Amyl alcohol                                                                            CH.sub.3 CH.sub.2 COH(CH.sub.3).sub.2                  2,2-Dimethyl-                                                                            tert-Butyl    (CH.sub.3).sub.3 CCH.sub.2 OH                          2-butanol                                                                      1-propanol                                                                               methanol                                                             3-Methyl- Methylisopropyl-                                                                             (CH.sub.3).sub.2 CHCHOHCH.sub.3                        2-butanol methanol                                                             1-Hexanol n-Hexyl alcohol                                                                              C.sub.6 H.sub.13 OH                                    4-Methyl- Methylisobutyl-                                                                              C.sub.6 H.sub.13 OH                                    2-pentanol                                                                               carbinol                                                             2-Methyl- Methyl amyl   C.sub.6 H.sub.13 OH                                    1-pentanol                                                                               carbinol                                                             2-Ethyl-  Pseudohexyl   C.sub.6 H.sub.13 OH                                    1-butanol alcohol                                                              1-Heptanol                                                                               n-Heptyl alcohol                                                                             C.sub.7 H.sub.15 OH                                    2-Heptanol (dl)                                                                          Methyl-n-amyl-                                                                               C.sub.7 H.sub.15 OH                                              carbinol                                                             1-Octanol n-Octyl alcohol                                                                              C.sub.8 H.sub.17 OH                                    2-Octanol (dl)                                                                           Capryl alcohol                                                                               C.sub.8 H.sub.17 OH                                    2-Ethyl-1-                                                                               2-ethyl-n-hexyl                                                                              C.sub.8 H.sub.17 OH                                    hexanol                                                                        Dimethyl-1-                                                                              iso-Octyl alcohol                                                                            C.sub.8 H.sub.17 OH                                    hexanol                                                                        1-Nonanol n-Nonyl alcohol                                                                              C.sub.9 H.sub.19 OH                                    2,6-Dimethyl-                                                                            Diisobutylcarbinol                                                                           C.sub.9 H.sub.19 OH                                    4-heptanol                                                                     2-Propen-1-ol                                                                            allyl alcohol CH.sub.2 ═CHCH.sub.2 OH                            Ethenol   vinyl alcohol CH.sub.2 ═CHOH                                     2-Propyn-1-ol                                                                            propargyl alcohol                                                                            CH═CCH.sub.2 OH                                    ______________________________________                                    

The borated compounds of these short-chain alcohols is prepared in the manner described for preparing the long-chain borated alcohols in the incorporated applications and patents.

The Diols

The diols used in this invention preferably are vicinal, and of the formula

    R.sup.3 (OH).sub.2

wherein R³ is a C₈ to C₃₀ hydrocarbyl group.

The Mono- or Polyamines

The borated amines useful in this invention are prepared by reacting an amine of the formula: ##STR2## wherein x is 0 or 2, R⁴, R⁵, R⁷ and R⁸ are hydrogen or a C₁ to C₃₀ hydrocarbyl groups including alkyl groups containing 6 to 20 carbon atoms, containing 6 to 20 carbon atoms and the corresponding members containing sulfur or additional oxygen, at least one of which is a hydrocarbyl group, i.e., is not hydrogen, and R⁶ is a C₂ to C₄ alkylene group, with a borating compound.

The hydrocaryl esters utilized herein have the formula

    R.sup.9 (COOR.sup.10).sub.n

wherein R⁹ and R¹⁰ are hydrocarbyl groups, or hydroxyhydrocarbyl groups, containing 1 to 40 carbon atoms, preferably 8 to 20 carbon atoms, at least one of R⁹ or R¹⁰ being a hydroxyhydrocarbyl group, and n is 1 to 5. The boron compound used for boronation is any of those noted previously.

The Borated Oxazoline Compounds

The oxazoline compounds used in this invention are believed to have the following generalized structure: ##STR3## where R¹¹ and R¹⁴ are hydrocarbyl or hydrocarbylene groups of one to fifty carbon atoms and optionally contain sulfur, oxygen, nitrogen, or halogen. Preferably R¹¹ and R¹⁴ are of eight to twenty carbon atoms. R¹² and R¹³ can be the same or different and can be hydrogen or have the generalized structure ##STR4## where R¹⁵ is hydrogen or a hydrocarbyl group of one to fifty carbon atoms. Preferably, at least one of R¹² or R¹³ is hydrogen available for boration.

More particularly, the product can be made by reacting molar amounts or more than molar amounts of a carboxylic acid of the formula

    R--COOH

with a hydroxyl amine such as tris(hydroxymethyl)aminomethane such that the oxazoline formed has the formula ##STR5## wherein R¹¹ is as defined above, followed by reacting the oxazoline with an appropriate borating agent.

The Borated Mercaptan Amine Aldehyde Products

The mercaptan amine aldehyde compounds that are borated for use in this invention are prepared as described in U.S. Pat. No. 4,486,321 and are mixtures of compounds, some of which have the following possible structures: ##STR6## wherein R¹⁶ is H or a C₁ to C₂₀ hydrocarbyl group, R¹⁷ is a C₂ to C₅ alkylene group, R¹⁸ is H or a C₁ to C₈ hydrocarbyl group (e.g., alkyl, alkenyl, cycloalkyl, alkaryl or aralkyl and R¹⁹ is a C₈ to C₃₀ hydrocarbyl group, preferably an alkyl group. R¹⁹ can be a straight chain or branched chain, with the straight chain being preferred.

The Borated Mannich Base (Phenol-Amine) Reaction Products

Borated Mannich base reaction products are disclosed in pending U.S. application Ser. No. 682,579, filed Dec. 17, 1984, which is a continuation of Ser. No. 445,883, filed Dec. 1, 1982. This application (Ser. No. 682,579) is incorporated herein by reference.

The borated Mannich base reaction product described in application Ser. No. 628,579 is made by borating a product made by reacting an aldehyde and an amine and one or more phenols of the formula: ##STR7## wherein R²⁰ is preferably hydrogen, but can be a C₁ to C₃₀ hydrocarbyl group, which may be an alkyl, alkenyl, aryl, alkaryl or aralkyl group. R²¹ is a hydrocarbyl group, preferably alkyl or alkenyl containing 4 to 20 atoms, and can additionally contain sulfur, oxygen and/or nitrogen atoms. R²¹ can also be a polymeric group having a molecular weight up to between 1000 and 2000 and can be polypropyl, polybutenyl, polyisobutyl or the like.

Aldehydes that can be used are the aliphatic aldehydes, typified by formaldehyde or paraformaldehyde, acetaldehyde, and aldol (-hydroxy butyraldehyde); aromatic aldehydes, such as benzaldehyde and heterocyclic aldehydes, such as furfural. The aldehyde may contain a substituent group such as hydroxyl, halogen, nitro and the like. In short, any substituent can be used which does not take a major part in the reaction. Preference, however, is given to the aliphatic aldehydes, formaldehyde being particularly preferred.

The amines to be used include those which contain a primary amino group. Preferably, these include saturated and unsaturated aliphatic amines containing 1 to 20 carbon atoms. They more specifically include those of the structural formula:

    R.sup.22 NH.sub.2

wherein R²² is a hydrocarbyl group having from 4 to 20 carbon atoms. These are preferably C₆ to C₁₈ straight or branched alkyl groups, but may be cyclic, the latter of which include cyclohexylamine. Straight chain amines are more preferred.

Other amines which can be used include:

(a) etheramines (hydrocarbyloxy hydrocarbyl amines) such as triisodecyloxypropyl amine and etheramines of the formula R²² OR²³ NH₂ where R²² is as stated above and R²³ is a C₁ to C₆ hydrocarbyl group;

(b) N-hydrocarbyl hydrocarbylene diamines or triamines such as N-oleyl-1,3 propylene or N-coco-1,2-ethylenediamine or amines of the structure ##STR8## where R²² and R²³ are as indicated above and Z is 1 to 3;

(c) etherdiamines (hydrocarbyloxy hydrocarbyl hydrocarbyl diamines) such as those of the structure ##STR9## where R⁷ and R⁹ are as indicated above and Z is 1 to 3;

Also useful are aryl-hydrocarbylene amines and diamines.

Hydroxyl Containing Amides

The hydroxyl-containing amides useful in this invention have the formula ##STR10## where R²⁴ is a hydrocarbyl group of 1 to 60 carbon atoms, preferably 2 to 50 carbon atoms, and most preferably 8 to 20 carbon atoms, including alkyl, alkenyl, alkoxyl, cycloalkenyl, cycloalkyl, alkaryl, aralkyl, etc. R can also contain oxygen, nitrogen or sulfur atoms.

R²⁵ and R²⁶ are each a hydrocarbylene group or a mixture of hydrocarbylene groups of 2 to 6 carbon atoms;

x is 0 to 15 and

y is 0 to 15 provided that x+y equals at least 1. Preferably x+y equals 2 to 10 and more preferably 2 to 6. The terms "hydrocarbyl" and "hydroxyhydrocarbyl" include alkyl, aryl, aralkyl, alkaryl and cycloalkyl groups and can also include oxygen or sulfur.

The Catechol Borate, Catechol-Amine-Borate, and Catechol-Alcohol-Amine Borate Compounds

The catechol borate and the borated catechol alcohol or borated catechol amine compounds are through to have the following structure: ##STR11## where R²⁷ and R²⁸ can each be hydrogen or C₁ -C₄₀ hydrocarbyl. R²⁷ and R²⁸ optionally can also contain sulfur, oxygen, nitrogen or other such groups as long as the presence of these elements does not negatively affect performance of the additive compound.

R²⁹ can be C₁ -C₄₀ hydrocarbyl and can contain, additionally, oxygen, sulfur and/or nitrogen-containing moieties.

R³⁰ can be C₁ -C₄₀ hydrocarbyl and can contain, additionally, oxygen, sulfur and/or nitrogen-containing moieties.

R³¹ can be boron and/or catechol and/or ester and/or hydroxyl-containing moieties.

Thus the family of catechol borates useful in this invention can be represented by the following nonlimiting generic structure: ##STR12## where R³² can be R²⁹, R³⁰, or R³¹, and can additionally contain oxygen, nitrogen, sulfur and boron as described above.

Organic Boron Compounds

Any substituent may be present in any of the above-mentioned organic borates provided that the substituent(s) do not negate the beneficial high-temperature dropping point improvement of the hydroxy-containing soap thickened grease. These substituents contained in the organic borates can include any elements of the periodic chart of the Elements.

We believe that the carbon number ranges (and molecular weights) outlined above are not restricting, but can be extended for use in greases. For instance, we believe that borates of alcohol ethoxylates derived from hydrocarbyl groups containing only one or two carbon atoms would be as effective as the higher molecular weight species described herein. Thus short chain diols and mono- or polyamines, or oxazolines or Mannich base products derived from hydrocarbyl groups of 1-10 carbon atoms could be used in this invention.

Likewise, we believe that higher molecular weight borates, including borates of polymeric materials having molecular weights of up to 10,000 to 20,000 or more can be used in this invention. These organic borates can also contain 1, 2, 3, 4 . . . 10 . . . or even 100 or more borate linkages per organic borate molecule.

A narrow class of thickening agents is preferred to make the grease of this invention. Included among the preferred thickening agents are those containing at least a portion of alkali metal or alkaline earth metal soaps or amines soaps of hydroxyl-containing fatty acids, fatty glycerides and fatty esters preferably having from 12 to abut 30 carbon atoms per molecule. The metals are typified by sodium, lithium, calcium and barium, with lithium being preferred. 12-hydroxystearic acid and glycerides and esters containing 12-hydroxystearates, 14-hydroxystearic acid, 16-hydroxystearic acid and 6-hydroxystearic acid are the preferred acids and fatty materials.

The entire amount of thickener need not be derived from the aforementioned preferred members. Significant benefit can be attained using as little as about 15% by weight of the hydroxystearate-containing thickener in the total thickener. A complementary amount, i.e., up to about 85% by weight of a wide variety of thickening agents can be used in the grease of this invention. Included among the other useful thickening agents are alkali and alkaline earth metal soaps of methyl-12-hydroxystearate, diesters of a C₄ to C₁₂ dicarboxylic acid and tall oil fatty acids. Other alkali or alkaline earth metal fatty acids containing from 12 to 30 carbon atoms and no free hydroxyl may be used. These include soaps of stearic and oleic acids. The aforementioned thickening agents can be produced in open kettles, pressurized vessels, or continuous manufacturing units. All of these production methods are commonly used for greases and have the necessary supporting equipment to process the grease during and after the manufacture of the thickener.

Other thickening agents include salt and salt-soap complexes as calcium stearate-acetate (U.S. Pat. No. 2,197,263), barium stearate acetate (U.S. Pat. No. 2,564,561), calcium, stearate-caprylate-acetate complexes (U.S. Pat. No. 2,999,065), calcium caprylate-acetate (U.S. Pat. No. 2,999,066), and calcium salts and soaps of low-, intermediate- and high-molecular weight acids and of nut oil acids.

Another group of thickening agents comprises substituted ureas, phthalocyamines, indanthrene, pigments such as perylimides, pyromellitdiimides, and ammeline, as well as certain hydrophobic clays. These thickening agents can be prepared from clays which are initially hydrophilic in character, but which have been converted into a hydrophobic condition by the introduction of long-chain hydrocarbon radicals into the surface of the clay particles prior to their use as a component of a grease composition, as, for example, by being subjected to a preliminary treatment with an organic cationic surface active agent, such as an onium compound. Typical onium compounds are tetraalkylammonium chlorides, such as dimethyl dioctadecyl ammonium chloride, dimethyl dibenzyl ammonium chloride and mixtures thereof. This method of conversion, being well known to those skilled in the art, is believed to require no further discussion, and does not form a part of the present invention.

In summary, it is essential to the practice of this invention, in which greases having vastly improved dropping points are obtained, that both of the above-mentioned ingredients be formulated into the composition. Thus:

First, with respect to the preparation of the grease, the total thickener will have at least about 15% by weight of a metal or non-metal hydroxy-containing soap therein, and there will be present from about 3% to about 20% by weight of total thickener based on the grease composition; and second, there will be added to the composition from about 0.01% to about 10% by weight thereof, preferably about 0.1% to about 2%, of a borated organic compound preferably containing oxygen, sulfur and/or nitrogen atoms or mixtures thereof, in which the borated organic compound preferably has been reacted in preferably at least an equimolar amount and, more preferably, an excess of a boron compound.

It has been noted that, when the hydroxy-containing thickener is used wit the borated organic compound or mixtures thereof, the dropping point of the grease is consistently unexpectedly higher than wit a grease from the same grease vehicle and the same borated organic compound, but with a different thickener, e.g., a non-hydroxy-containing thickener. This absence of dropping point elevation is demonstrated in Examples 8, 16, 22, 28, 39, 47, 54, 61, 68 and 77. Thus, the broad invention is to a grease composition comprising the two components mentioned.

In general, the reaction products of the present invention may be employed in any amount which is effective for imparting the desired degree of friction reduction, antiwear activity, antioxidant activity, high temperature stability or antirust activity. In many applications, however, the borated organic compound and the phosphorus- and/or sulfur-containing compound(s) are effectively employed in combined amounts from about 0.02% to about 20% by weight, and preferably from about 0.2% to about 4% of the total weight of the composition.

The greases of the present invention can be made from either a mineral oil or a synthetic oil, or mixtures thereof. In general, mineral oils, both paraffinic, naphthenic and mixtures thereof, may be of any suitable lubricating viscosity range, as for example, from about 45 SSU at 100° F. to about 6000 SSU at 100° F., and preferably from about 50 to about 250 SSU at 210° F. These oils may have viscosity indexes ranging to about 100 or higher. Viscosity indexes from about 70 to about 95 are preferred. The average molecular weights of these oils may range from about 250 to about 800. In making the grease, the lubricating oil from which it is prepared is generally employed in an amount sufficient to balance the total grease composition, after accounting for the desired quantity of the thickening agent, and other additive components to be included in the grease formulation.

In instances where synthetic oils are desired, in preference to mineral oils, various compounds of this type may be successfully utilized. Typical synthetic vehicles include polyisobutylene, polybutenes, hydrogenated polydecenes, polypropylene glycol, polyethylene glycol, alkyl aromatics such as alkyl benzenes and naphthalenes, trimethylol propane esters, neopentyl and pentarythritol esters, di(2-ethylhexyl) sebacate, di(2-ethylhexyl) adipate, dibutyl phthalate, fluorocarbons, silicate esters, silanes, esters of phosphorus-containing acids, liquid ureas, ferrocene derivatives, hydrogenated synthetic oils, chain-type polyphenyls, siloxanes and silicones (polysiloxanes), alkyl-substituted diphenyl ethers typified by a butyl-substituted bis(p-phenoxy phenyl) ether, phenoxy phenylethers.

The metallic soap grease compositions containing one or more of the borated organic compounds, and, optionally, one or more of the sulfur and phosphorus combinations described herein provide advantages in increased dropping point, improved grease consistency properties, antirust characteristics and potential antifatigue, antiwear and antioxidant benefits unavailable in any of the prior greases known to us. The grease of this invention is unique in that it can be preferably manufactured by the admixture of additive quantities of the organic borates or oil concentrates or dispersions of such organic borates to the fully formed soap grease after completion of saponification.

ALCOHOL BORON COMPOUNDS Example Preparation of Tri(4-methyl-2-pentyl) Borate

Approximately 306 grams of 4-methyl-2-pentanol, 100 grams of toluene, and 62 grams of boric acid were charged to a 2-liter glass reactor having an inert nitrogen atmosphere and equipped with heater, agitator, and Dean-Stark tube with condenser. The reactants were heated up to about 155° C. for a period of about 5 hours with agitation unit water evolution during azeotropic distillation ceased. Approximately 52 grams of water was collected. The product was vacuum topped at about 155° C. to remove volatile solvent and filtered hot through diatomaceous earth to form a clear, water-white liquid.

Tributyl Borate

A commercial grade of tributyl borate was also used in the tests reported. It could have been made in the laboratory by the reaction of n-butanol with boric acid, optionally in the presence of a solvent such as benzene.

Example 2

A lithium hydroxystearate grease thickener was prepared by saponification of a mixture containing 12-hydroxystearic acid (50%) and the tri-glyceride thereof (50%) with lithium hydroxide in a mineral oil vehicle (ISO 150 viscosity grade of a 70/30 mixture of naphthenic and paraffinic stocks) at about 350° F. in a closed contactor. After depressing and dehydration of the thickener in an open kettle sufficient mineral oil was added to reduce the thickener content to about 9.0%. After cooling to 210° F., a typical grease additive package, consisting of an amine antioxidant, phenolic antioxidant, metallic dithiophosphate, sulfur-containing metal deactivator and nitrogen containing antirust additives, was added. The dropping point of thise base grease was 395° F.

Example 3

Two weight percent of the borated (4-methyl-2-pentyl) alcohol of Example 1 were added to the base grease of Example 2 at about 110° to about 115° C.

EAMPLE 4

Two weight percent of the tributyl borate described above were added to the base grease of Example 2 at about 110° to 115° C.

Example 5

A lithium hydroxystearate grease thickener was prepared by saponification of a mixture containing 12-hydroxystearic acid (50%) and the tri-glyceride thereof (25%) and 25% of C₂₂ fatty acids containing no OH groups with lithium hydroxide in a mineral oil vehicle (ISO 150 viscosity grade of a 70/30 mixture of naphthenic and paraffinic stocks) at about 350° F. in a closed contactor. After depressuring and dehydration of the thickener in an open kettle sufficient mineral oil was added to reduce the thickener content to about 8%. The dropping point of this grease was 407° F. (208° C.). This grease containing no phosphorus or sulfur additives.

Example 6

Two weight percent of the tributylborate described above as added to the base grease of Example 5 at about 110° C. to 115° C.

Example 7

A lithium stearate grease thickener was prepared by saponification of stearic acid with lithium hydroxide in a mineral oil vehicle (ISO 150 viscosity grade of a 70/30 mixture of naphthenic and paraffinic stocks) at about 350° F. in a closed contactor. After depressurizing and dehydration of the thickener in an open kettle sufficient mineral oil was added to reduce the thickener content to about 10.0%. The grease thickener of this example contained no hydroxyl groups in the lithium stearate soap. The dropping point of this grease was 403° F. (206° C.).

Example 8

Two weight percent of the tributyl borate described above and two wt percent zinc dialkyl dithiophosphates (derived from mixed C₃ secondary (isopropyl) and C₆ primary alcohols) was added to the base grease of Example 7 at about 110° C. to 115° C.

ASTM D2265 Dropping Point Test results for the various greases are shown in Table V.

                  TABLE I                                                          ______________________________________                                                                D2265                                                   Sample                 Dropping Point °C.                               ______________________________________                                         Base grease of Example 2 (containing amine                                                            202° C.                                          antioxidant, phenolic antioxidant, 1.5%                                        xinc dithiophosphate and sulfur-containing                                     metal deactivator and nitrogen                                                 containing antirust additives                                                  Grease of Example 3    323° C.                                          Grease of Example 4    317° C.                                          Grease of Example 5    208° C.                                          Grease of Example 6    253° C.                                          Grease of Example 7    206° C.                                          Grease of Example 8    204° C.                                          ______________________________________                                    

As can be seen from above (Ex. 7 and 8), no dropping point improvement is derived unless a portion of the thickener contains a hydroxyl group in the soap. As can also be seen above, the phosphorus and/or sulfur sources are not required, but can often enhance the dropping point improving properties of these borates when admixed with a grease manufactured with a hydroxyl-containing thickener.

The above mentioned zinc dithiophosphate was derived from mixed C₃ secondary (isopropyl) and C₆ primary alcohols.

In order to more clearly set forth applicants' invention the data disclosed in the copending parent application has been abstracted into the body of data as shown in Table II. From this table it is readily discernible that the combination of a borated organic compound and a hydroxy bearing thickener results in a grease having a substantially increased dripping point temperature.

Table III is a direct comparison of an additive fuel lithium hydroxystearate thcikened base grease; the base grease containing (1) a zinc-dithiophosphate additive; (2) a zinc dithiophosphate additive and a organic borate in accordance with the invention and (3) a zinc dithiophosphate additive and boric acid.

It can be readily seen from Table III that the addition of the organic borate provides grease compositions having a much improved dropping point.

Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled int he art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims.

                                      TABLE II                                     __________________________________________________________________________                          % Amount of                                                                           % of  Percent of                                                                              Dropping                                                 Borated                                                                               Hydroxy                                                                              Added Zinc                                                                              Point                               Item Number                                                                           Borated Compound                                                                             Compound                                                                              Thickener                                                                            Thiophosphorate                                                                         °C.                          __________________________________________________________________________      3     Alcohol Ethoxylate                                                                           0      9.0   1.5      202                                  4     "             2      9.0   1.5      237                                  5     "             2      9.0   1.5      305                                  6     "             0      0     0        209                                  7     "             0      4.5   0.75     190                                  8     "             2      0     0        207                                 10     Alcohols      0      9     1.5      202                                 11     "             2      9     1.5      323                                 12     "             2      9     1.5      317                                 13     "             0      8     0        208                                 14     "             2      8     0        253                                 15     "             0      0     0        206                                 16     "             2      0     2        204                                 18     "             0      9     1.5      201                                 19     "             2      9     1.5      327                                 20     "             0      0     0        209                                 21     "             0      41/2 appx.                                                                           0.75     190                                 22     "             2      0     0        207                                 24     Organic Diols 0      9     1.5      201                                 25     "             2      9     1.5      305                                 26     "             0      0     0        209                                 27     "             0      4.5   0        190                                 28     "             2      0     0        207                                 31     Organic Diamines                                                                             0      8     0        199                                 32     "             0      9     1.5      200                                 33     "             0.5    9     1.5      310                                 34     "             1.0    9     1.5      300                                 35     "             0.5    8     0        236                                 36     "             2      8     0        258                                 37                   0      0              209                                 38                   0      4.5            190                                 39                   2      0              207                                 42     Hydroxyl-Containing Ester                                                                    0      9     1.5      202                                 43     "             2      9     1.5      240                                 44     "             2      9     1.5      290                                 45     "             0      0     0        209                                 46     "             0      4.5   .75      190                                 47     "             2      0     0        207                                 48     Oxazoline Compounds                                                                          0      9     1.5      202                                 49     "             0      10    0        202                                 50     "             0      0     0        207                                 51     "             2      10    0        232                                 52     "             2      10    0        267                                 53     "             2      10    1.5      319                                 54     "             2      0     0        201                                 55     Phenolic Amine Compounds                                                                     0      9     1.5      202                                 56     "             0      10    0        202                                 57     "             0      0     0        207                                 59     "             2      10    0        264                                 60     "             2      10    1.5      299                                 61     "             2      0     0        203                                 62     Hydroxyl-Containing Amides                                                                   0      9     1.5      202                                 63     "             0      10    0        202                                 65     "             2      10    0        253                                 66     "             2      10    1.5      307                                 67     "             0      0     0        207                                 68     "             2      0     0        201                                 69     Catechol Compounds                                                                           0      9     1.5      202                                 70     "             0      10    0        202                                 71     "             0      0     0        207                                 72     "             2      10    0        243                                 73     "             2      10    0        254                                 74     "             2      9     1.5      302                                 75     "             2      10    0        302                                 76     "             2      9     1.5      309                                 77     "             2      0     0        199                                 __________________________________________________________________________      *Examples 10-16 are examples 2-8 described in this specification.        

                  TABLE III                                                        ______________________________________                                                                  ASTMD-                                                                         2265                                                                           DROP-                                                                          ING PT,                                                                        °F.                                            ______________________________________                                         Base grease - Lithium hydroystearate thickened,                                                           398                                                 150 VG 150, 9.5% fatty matter, Additive-free                                   Above grease w/1.5% zinc dithiophosphate                                                                  393                                                 Above grease w/1.5% zinc dithiophosphate and 1.5%                                                         542                                                 borated glycerol monopleate (borated GMO blended                               270° F.)                                                                Above grease w/1.5% zinc dithiophosphate and 0.5%                                                         419                                                 boric acid (boric acid blended 270° F.)                                 ______________________________________                                          Note.sup.1 0.5% boric acid provides 2.7 times the boron level as 1.5%          above borated GMO                                                         

We claim:
 1. An improved grease composition comprising a major proportion of a lubricating component and containing a minor amount consisting of:(a) a borated derivative of an organic compound; (b) an alkali or alkaline earth metal or amine derivative of a hydroxy-containing or polyhydroxy-containing soap thickener; said borated organic compound and said hydroxy-containing thickener each being present in an amount sufficient to increase the dropping point over the dropping point of a grease without said borated organic compound.
 2. The composition of claim 1 wherein said borated derivative is present in said grease composition in an amount of between about 0.2 and about 10 percent by weight.
 3. The composition of claim 1 wherein the total amount of thickener added is between about 3 and about 20 percent by weight of the total composition.
 4. The composition of claim 3 wherein the thickener contains at least 15 percent by weight of hydroxy-containing thickener.
 5. The composition of claim 1 wherein said metal is selected from lithium or calcium.
 6. The composition of claim 5 wherein said hydroxy-containing soap thickener is lithium or calcium hydroxystearate.
 7. The composition of claim 5 wherein said hydroxy-containing soap thickener is calcium hydroxysterate.
 8. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting an alkoxylated alcohol of the formula

    (RO)(R.sup.1 O).sub.x H

wherein R is a hydrocarbyl group or a mixture of hydrocarbyl groups, containing form 1 to 50 carbon atoms, R¹ is a C₂ to C₄ hydrocarbylene group and x is from 1 to 7 with a boron compound.
 9. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting an alcohol of the formula

    R.sup.2 OH

wherein R² is a hydrocarbyl group, or mixture thereof, containing from 1 to 30 carbon atoms, with a boron compound.
 10. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting a diol of the formula

    R.sup.3 (OH).sub.2

wherein R³ is a hydrocarbyl group containing from 2 to 30 carbon atoms with a boron compound.
 11. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting an amine of the formula ##STR13## wherein x is 0 to 2, R⁴, R⁵, R⁷ and R⁸ are hydrogen or hydrocarbyl groups containing from 1 to 30 carbon atoms, hydroxyalkyl groups containing 2 to 4 carbon atoms, a polyalkoxylated group containing 6 to 20 carbon atoms or the latter group containing sulfur or additional oxygen, at least one of R⁴, R⁵, R⁷ and R⁸ being a non-hydrogen group and R⁶ is a C₂ to C₄ alkylene group, with a boron compound.
 12. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting an ester of the formula

    R.sup.9 (COOR.sup.10).sub.n

wherein n is 1 to 5 and R⁹ and R¹⁰ are hydrocarbyl or hydroxyhydrocarbyl groups containing 1 to 20 carbon atoms, at least one of R⁹ and R¹⁰ being a hydroxyhydrocarbyl group with a boron compound.
 13. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting an oxazoline of the generalized structure ##STR14## where R¹¹ is a hydrocarbyl or hydrocarbylene group of one to fifty carbon atoms, at least one of R¹² or R¹³ is hydrogen and the other is hydrogen or has the generalized structure ##STR15## where R¹⁴ is a hydrogen or a hydrocarbyl group of one to fifty carbon atoms with a boron compound.
 14. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting an oxazoline of the generalized structure ##STR16## where R¹⁷ is a hydrocarbyl or hydrocarbylene group of one to fifty carbon atoms, at least one of R¹⁵ or R¹⁶ is hydrogen and the other is hydrogen or has the generalized structure ##STR17## where R¹⁸ is hydrogen or a hydrocarbyl group of one to fifty carbon atoms with a boron compound.
 15. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting an amine with an aldehyde and a phenol or mercaptan and subsequently reacting the resulting product with a boron compound, the hydroxy-containing thickener and borated amine condensation product being present in sufficient quantities to effect an increase in the dropping point of said grease.
 16. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting an hydroxyl-containing amide having the structural formula: ##STR18## wherein R¹⁹ is a hydrocarbyl group of 1 to 60 carbon atoms and can additionally contain sulfur, oxygen and/or nitrogen;R²⁰ and R²¹ are each a hydrocarbylene group or a mixture of hydrocarbylene groups of 2 to 6 carbon atoms; x is 0 to 15, and y is 0 to 15, provided that x+y equals least 1 with a boron compound.
 17. The composition of claim 1 wherein the borated derivative is the reaction product made by reacting a catechol compound having the structure: ##STR19## where R²² and R²³ are each hydrogen or a C₁ -C₄₀ hydrocarbyl radical and R²⁴ is(1) a C₁ -C₄₀ hydrocarbyl radical which can contain additionally oxygen, nitrogen, sulfur or boron; (2) an NR²⁵ group where R²⁵ is a C₁ -C₄₀ hydrocarbyl group which can contain additionally oxygen, sulfur or nitrogen atoms; (3) an OR²⁶ group where R²⁶ is a C₁ -C₄₀ hydrocarbyl group which can contain additionally oxygen, sulfur or nitrogen atoms; or (4) an OR²⁵ group where R²⁵ is boron, or a catechol, ester or hydroxyl-containing moiety and can contain additionally oxygen, nitrogen, sulfur or boron with a boron compound.
 18. The composition of claim 1 wherein the borated derivative additionally contains oxygen, sulfur, and/or nitrogen or mixtures thereof which is reaction with a borating agent.
 19. The composition of claim 1 wherein the borated derivative of an organic compound contains additionally any of the elements of the Periodic Table of the Elements, except zinc.
 20. The composition of claim 1 wherein the borated derivative is a polymeric organic borate.
 21. The composition of claim 7 wherein hydrocarbyl is selected from the group consisting of alkyl, alkaryl alkenyl and alkyl or mixtures thereof.
 22. The composition of claim 19 wherein the borated derivative of an organic compound contains additionally phosphorus.
 23. A method for elevating the dropping point of a grease composition comprising incorporating into said grease product an organic boron compound, and an alkali for alkaline earth metal or amine derivative of a hydroxy-containing or polyhydroxy-containing soap thickener.
 24. The method of claim 23 wherein the grease product is comprised of a synthetic oil selected from the group consisting of polyglycols, synthetic hydrocarbons, alkyl aromatics, dibasic acid esters, polyol esters, phosphate esters or mixtures thereof.
 25. The method of claim 24 wherein said metal is selected from lithium or calcium.
 26. The method of claim 24 wherein the hydroxy-containing soap thickener is at least 15% by weight of the total thickener in said grease composition.
 27. The method of claim 23 wherein the borated derivative additionally contains oxygen, sulfur and/or nitrogen or mixtures thereof is reactive with a borating agent.
 28. A method of claim 23 wherein the borated derivative contains additionally any of the elements of the Periodic Table of the Elements, except zinc.
 29. The method of claim 24 wherein the borated organic compound is a polymeric organic borate.
 30. The method of claim 28 wherein the borated derivative additionally contains phosphorus.
 31. A method for making grease wherein a liquid lubricant is mixed with a thickening agent, the improvement comprising adding to said grease a borated organic compound and an alkali or alkaline earth metal or amine derivative of an hydroxy-containing thickener.
 32. The method of claim 31 wherein said metal is selected from lithium or calcium.
 33. The method of claim 31 wherein the borated derivative additionally contains oxygen sulfur and/or nitrogen as mixtures thereof which is reactive with a borating agent.
 34. The method of claim 31 wherein the borated derivative contains additionally any of the Periodic Table of the Elements, except zinc.
 35. A method of claim 31 wherein the borated organic compound is a polymeric organic borate.
 36. An improved grease composition comprising a major proportion of a lubricating component and:(a) a borated derivative of an organic compound containing an hydroxyl, epoxide, thiol or nitrogen moiety which is reactive with a borating agent, and (b) a hydroxy-containing or polyhydroxy- containing soap thickener; said borated organic compound and said hydroxy-containing thickener each being present in an amount sufficient to increase the dropping point over the dropping point of a grease without said borated organic compound.
 37. A method for elevating the dropping point of a grease composition comprising incorporating into said grease product a borated derivative of an organic compound containing an hydroxyl, epoxide, thiol and/or nitrogen and a hydroxy-containing or polyhydroxy-containing soap thickener.
 38. An improved grease composition comprising a major proportion of a lubricating component and:(a) a borated derivative of an organic compound containing an hydroxyl, epoxide, thiol or nitrogen moiety which is reactive with a borating agent, and (b) a hydroxy-containing or polyhydroxy- containing soap thickener; said borated organic compound and said hydroxy-containing thickener each being present in an amount sufficient to increase the dropping point over the dropping point of a grease without said borated organic compound.
 39. A method for elevating the dropping point of a grease composition comprising incorporating into said grease product an organic compound containing an hydroxyl, thiol and/or nitrogen and a hydroxy-containing or polyhydroxy-containing soap thickener. 